Cellulose derivative composition



Patented Feb. 13, 1934 CELLULOSE DERIVATIVE COMPOSITION No Drawing. Original application May 19, 1931,

Serial No. 538,613.

Divided. and this application May 14., 1932. Serial No. 611,437

8 Claims.

This invention relates to new cellulose derivative compositions, and more particularly, to cellulose derivative compositions containing polyhydric alcohol esters of halogenated fatty acids as plasticizers. This application is a division of applicants copending application Serial No. 538,613, filed May 19, 1931, Esters of halogenated fatty acids and compositions including same.

An object of the present invention is to provide new cellulose derivative compositions having improved properties. A further and more particular object is to provide new cellulose derivative compositions especially advantageous for use as plastic or coating compositions. Other objects of the invention will be apparent from the description given hereinafter.

These objects are accomplished according to the present invention by the use of polyhydric alcohol esters of halogenated acids as plasticizers in cellulose derivative compositions.

The esters coming within the scope of the present invention may be prepared by reacting the polyhydric alcohols with the halogenated fatty acids at an elevated temperature, preferably between 80-2'l0 C., and removing the water formed by said reaction at substantially the rate it is formed. This reaction may be carried out in the presence of a solvent for the reactants and a catalyst such as sulphuric acid, if desired.

In carrying out this reaction, the proportion of alcohol to acid may be varied greatly, but the acid should always be in slight excess of the amount required to combine with the alcohol to form the desired ester.

The following examples are given to illustrate the method of preparation of several of these esters:-

Example 1 Ethylene di-chZoroacetate.-19O grams of glycol and 600 grams of chloraoetic acid were heated together until the boiling point reached 250 C., and held at 250 C. until no more water was evolved. The mixture was cooled, poured into water, and washed with dilute potassium carbonate solution to remove the excess acid. The product was then distilled in vacuo, 545 grams distilling over between 165 and 190 C. at 10 mm. pressure.

Example 2 Glyceryl ali-chloroacetate.-A mixture of 200 grams glycerol and 500 grams chloroacetic acid was heated until the boiling point reached 250 0., and was held at 250 C. until no more water was evolved. The mixture was treated as in Example 1, 3'70 grams distilling over between 195 and 215 C. at 6 mm. pressure.

Example 3 Example 4 methylene glycol chloroacctata-A mixture of 200 grams diethylene glycol and 400 grains chloroacetic acid was heated until the boiling point reached 250 (3., and was held at 250 C. until no more water was evolved. The mixture was distilled in vacuo, 370 grams distilling over between 180 and 210 C. at 6mm. pressure.

Example 5 G-Zyceryl dl-bromoacetatc.A mixture of 33 grams glycerol and 100 grams brornoacetic acid was heated until the boiling point reached 250 C., and was held at 250 C. until no more water was evolved. The mixture was treated as in Example 1, '70 grams distilling over between 200 and 250 C. at 8 mm. pressure.

Example 6 Glyceryl cli-bromopropionatc.-A mixture of 30 grams glycerol and 100 grams alpha bromopropionic acid was heated until the boiling point reached 250 C., and was held at 250 C. until no more water was evolved. The product was treated as in Example 1, 85 grams distilling over between 210 and 260 C. at 4 mm. pressure.

Example 7 Glyccryl di-bromobutyrata-A mixture of 2'7 grams glycerol and 100 grams alpha bromobutyric acid was heated until the boiling point reached 250 C., and was held at 250 C. until no more water was evolved. The product was treated as in Example 1, 70 grams distilling over between 200 and 260 C. at 3 mm. pressure.

Erample 8 Sorbitol hera-chloroacetate.Amixture of grams sorbitol and 100 grams chloroacetic acid was heated until the boiling point reached 170 C., and was held at 170 C. until no more water was evolved. The mixture was poured into water, the oily layer was dissolved in alcohol, enough calcium carbonate was added to neutralize the excess acid, and the solution was then decolorized with Carboraffin. After removal of the solvent, a pale amber colored syrup resulted.

Example 9 Pentwerythritol di-chloroxcetate.A mixture of 78 grams pentaerythritol and 92 grams chloracetic acid was heated until the boiling point reached 195 C., and was held at 195 C. until no more water was produced. The product was treated as in Example 8, a viscous amber oil resulting.

The esters disclosed in the above examples are more or less viscous oils having a water white to pale amber color. They are higher boiling and less soluble in water than esters prepared from the corresponding unsubstituted acids and are readily soluble in alcohol, acetone, ethyl acetate, butyl acetate, benzene, xylene, and the lilte solvents and diluents commonly used in cellulose derivative compositions adapted to be employed as plastics or lacquers. These esters are compatible when mixed in equal proportions with cellulose nitrate, cellulose acetate, benzyl cellulose, or ethyl cellulose, and give tough, flexible films. Films plasticized with these esters do not darken any more than films plasticized with dibutyl phthalate and other well known plasticizers, thus indicating the comparative stability of the halgen atoms in these esters. One of the most interesting and valuable properties of these plasticizers, however, is their ability to plasticize cellulose acetate films and render them substantialiy permanently flexible. Their excellent plasticizing action is further exemplified by the fact that they will allow the preparation or" mixed cellulose acetate-cellulose nitrate compositions from which completely compatible films and molded articles can be made.

It is preferred to use poiyhydric alcohols having from 2-6 carbon atoms inclusive and fatty acids having 2-4 carbon atoms inclusive, although the invention is not limited to such alcohols and acids, as alcohols and acids having a greater number of carbon atoms may be used. It is preferred to use chlorine or bromine as the halogen constituent of the fatty acid because of the avail ability and cheapness or" these halogens, but fatty acids containing iodine or fluorine atoms are in cluded within the scope of the invention. Pref-- erably, monohalogen substituted fatty acids are used, and of these, those compounds in which the halogen is in the alpha position to the car- 'boxyl group of the acid are preferred.

The following examples are given to illustrate cellulose derivative compositions including the esters above described:

Example 10 Parts Cellulose nitrate 2 Damar 3 Glyceryl di-chloroacetate 4 Castor oil 2.6 Solvent 166.5

Example 11 Parts Cellulose nitrate 12 Damar 3 Ethylene chloroacetate 1 6.6 Solvent 166.5

Example 12 Parts Cellulose acetate 12.0 Diethylene glycol chloroacetate 6.0 Solvent 182.0

Example 13 Parts Cellulose nitrate 12 Pigment 16.3 Resin 3.5

Oil 2.6 Glyceryl di-chlo-roa-cetate 4.0 Solvent 161.6

Example 14 Parts Benzyl cellulose 2 Glyceryn tri-chloroacetate 1 Solvent 12 The above lacquers and enamels give films which dry tack-free in five minutes, are tough and flexible, and are very durable.

Example 15 Parts Cellulose nitrate 1 Cellulose acetate 1 Glyceryl di-chloroacetate 1 Solvent 15 The above composition gives a tough, flexible film which is much less inflammable than ordinary cellulose nitrate films. The film is completely compatible, which shows the remarkable plasticizing effect the glyceryl di-chloroacetate possesses for cellulose esters, particularly the acetate. Similar compositions in which the glyceryl di-chloroacetate is replaced by one of the other esters hereinbefore described also gives compatible films of excellent properties.

By the term solvent used in the foregoing examples included any of the well known solvent mixtures of alcohols, esters, such as ethyl, butyl, and ainyl acetate, and hydrocarbons such as benzene, toluene, and xylene. mixtures can be varied widely as is well understood in the art.

Other plasticizers may be used to replace in part the plasticizers given in the foregoing examples. For instance, triacetin, phthalate, acetanilide, triphenyl phosphate, and similar common plasticizers may be used in cellulose acetate compositions and camphor, dibutyl phthalate, and tricresyl phosphate may be used in the cellulose nitrate compositions. Also resins such as damar, ester gum, and various synthetic resins, such as the polyhydric alcoholpolybasic acid resins, may be used in these compositions.

The following examples are given to illustrate plastic compositions including the esters coming within the scope of the present invention:

Glyceryl tri chloroacetate 20 The solvent dimethyl Example 19 Parts Cellulose butyrate 100 Diethylene glycol chloroacetate Example 20 Parts Cellulose propionate 100 Glyceryl di-bromopropionate Example 21 Parts Cellulose aceto-butyrate 100 Glyceryl di-bromobutyrate 20 Example 22 Parts Cellulose acetate 100 Glyceryl di-chloroacetate 60 Filler (including color) 200 Example 23 Parts Cellulose nitrate 100 Diethylene glycol chloroacetate 50 Filler (including color) 200 Example 24 Parts Cellulose n1trate 100 Cellulose acetate 100 Glyceryl di-chloroacetate 90 The compositions illustrated in the above examples may be prepared with or without the usual volatile solvents or diluents, such as alcohol for the cellulose nitrate compositions, acetone for the cellulose compositions, and toluolalcohol mixtures for the ether compositions. As in the case of the coating compositions, so with the plastic compositions, the plasticizers may be replaced in part by known plasticizers, if desired.

The compositions coming within the scope of this invention may be used for lacquers for coatting metal and wood, dopes for coating fabrics, and in plastic compositions to be used in the preparation of toilet ware, novelties, sheeting, rods, tubes, and the like.

The use of these esters in cellulose derivative compositions is advantageous because of the fact that they are water-resistant and. give waterresistant, tough, flexible films which retain their flexibility indefinitely due to the low vapor pressure of the esters. The use of these esters as plasticizers for cellulose acetate is particularly advantageous due to their exceptional plasticizing action on cellulose acetate. Also the fact that these esters can be used to produce completely compatible films comprising cellulose nitrate and cellulose acetate is a marked advantage, as such films are fire resistant and extremely tough and durable.

As many apparently and widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that I do not limit myself to the specific embodiments thereof except as defined in the appended claims.

I claim:

1. A composition comprising a cellulose derivative and an ester formed by esterifying a halogenated fatty acid having from 2-4 carbon atoms, inclusive, with a polyhydric alcohol having from 2-6 carbon atoms, inclusive.

2. A composition comprising a cellulose derivative and glyceryl di-chloroacetate.

3. A composition comprising a cellulose derivative and glyceryl tri-chloroacetate.

4. A composition comprising a cellulose derivative and ethylene di-chloroacetate.

5. A composition comprising cellulose acetate and a polyhydric alcohol ester of a halogenated fatty acid, said acid having from 24 carbon atoms.

6. A composition comprising cellulose nitrate and a polyhydric alcohol ester of a halogenated fatty acid, said acid having from 2-4 carbon atoms.

7. A composition comprising a cellulose ether 115 and a polyhydric alcohol ester of a halogenated fatty acid, said acid having from 24 carbon atoms.

8. A composition comprising cellulose acetate, cellulose nitrate, and a polyhydric alcohol ester 120 of a halogenated fatty acid, said acid having from 2-4 carbon atoms.

EMMET'I'E F. IZARD. 

